JP6093716B2 - Resin composition for sealant, laminated film and packaging bag - Google Patents
Resin composition for sealant, laminated film and packaging bag Download PDFInfo
- Publication number
- JP6093716B2 JP6093716B2 JP2013553278A JP2013553278A JP6093716B2 JP 6093716 B2 JP6093716 B2 JP 6093716B2 JP 2013553278 A JP2013553278 A JP 2013553278A JP 2013553278 A JP2013553278 A JP 2013553278A JP 6093716 B2 JP6093716 B2 JP 6093716B2
- Authority
- JP
- Japan
- Prior art keywords
- sealant
- resin composition
- layer
- cycloolefin
- laminated film
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000000565 sealant Substances 0.000 title claims description 51
- 239000011342 resin composition Substances 0.000 title claims description 27
- 238000004806 packaging method and process Methods 0.000 title claims description 15
- 229920000089 Cyclic olefin copolymer Polymers 0.000 claims description 44
- -1 cyclic olefin Chemical class 0.000 claims description 34
- 229920001577 copolymer Polymers 0.000 claims description 23
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 10
- 125000003518 norbornenyl group Chemical group C12(C=CC(CC1)C2)* 0.000 claims description 7
- 229920000642 polymer Polymers 0.000 claims description 7
- 239000000654 additive Substances 0.000 claims description 4
- 230000000996 additive effect Effects 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 150000001925 cycloalkenes Chemical class 0.000 claims 1
- 239000010410 layer Substances 0.000 description 72
- 230000004888 barrier function Effects 0.000 description 14
- 238000007789 sealing Methods 0.000 description 12
- 239000007789 gas Substances 0.000 description 11
- 239000003795 chemical substances by application Substances 0.000 description 10
- 239000000047 product Substances 0.000 description 9
- 239000012812 sealant material Substances 0.000 description 9
- 125000004432 carbon atom Chemical group C* 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 239000012790 adhesive layer Substances 0.000 description 6
- 238000001125 extrusion Methods 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 238000001179 sorption measurement Methods 0.000 description 6
- 125000000962 organic group Chemical group 0.000 description 5
- 229920006280 packaging film Polymers 0.000 description 5
- 239000012785 packaging film Substances 0.000 description 5
- 229920005672 polyolefin resin Polymers 0.000 description 5
- 230000003014 reinforcing effect Effects 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- ZAKOWWREFLAJOT-CEFNRUSXSA-N D-alpha-tocopherylacetate Chemical compound CC(=O)OC1=C(C)C(C)=C2O[C@@](CCC[C@H](C)CCC[C@H](C)CCCC(C)C)(C)CCC2=C1C ZAKOWWREFLAJOT-CEFNRUSXSA-N 0.000 description 4
- 239000004480 active ingredient Substances 0.000 description 4
- ZAKOWWREFLAJOT-UHFFFAOYSA-N d-alpha-Tocopheryl acetate Natural products CC(=O)OC1=C(C)C(C)=C2OC(CCCC(C)CCCC(C)CCCC(C)C)(C)CCC2=C1C ZAKOWWREFLAJOT-UHFFFAOYSA-N 0.000 description 4
- 238000009820 dry lamination Methods 0.000 description 4
- 239000011888 foil Substances 0.000 description 4
- 230000009477 glass transition Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 229940042585 tocopherol acetate Drugs 0.000 description 4
- 238000007740 vapor deposition Methods 0.000 description 4
- WKBPZYKAUNRMKP-UHFFFAOYSA-N 1-[2-(2,4-dichlorophenyl)pentyl]1,2,4-triazole Chemical compound C=1C=C(Cl)C=C(Cl)C=1C(CCC)CN1C=NC=N1 WKBPZYKAUNRMKP-UHFFFAOYSA-N 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 238000004873 anchoring Methods 0.000 description 3
- 239000002537 cosmetic Substances 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 239000000796 flavoring agent Substances 0.000 description 3
- 235000019634 flavors Nutrition 0.000 description 3
- 235000013305 food Nutrition 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 229910052809 inorganic oxide Inorganic materials 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 239000004711 α-olefin Substances 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N 1-Heptene Chemical compound CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 description 2
- 239000004677 Nylon Substances 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 229920006125 amorphous polymer Polymers 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 230000004927 fusion Effects 0.000 description 2
- 238000010030 laminating Methods 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- 239000006210 lotion Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 239000005026 oriented polypropylene Substances 0.000 description 2
- 239000005022 packaging material Substances 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- 239000012466 permeate Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 230000002787 reinforcement Effects 0.000 description 2
- WLTSXAIICPDFKI-FNORWQNLSA-N (E)-3-dodecene Chemical compound CCCCCCCC\C=C\CC WLTSXAIICPDFKI-FNORWQNLSA-N 0.000 description 1
- GVRWIAHBVAYKIZ-FNORWQNLSA-N (e)-dec-3-ene Chemical compound CCCCCC\C=C\CC GVRWIAHBVAYKIZ-FNORWQNLSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- 125000004974 2-butenyl group Chemical group C(C=CC)* 0.000 description 1
- 238000006677 Appel reaction Methods 0.000 description 1
- 229920002799 BoPET Polymers 0.000 description 1
- WLQKHRHCTSEXTL-UHFFFAOYSA-N C1C2CCC1C=C2.C1C2CCC1C=C2 Chemical compound C1C2CCC1C=C2.C1C2CCC1C=C2 WLQKHRHCTSEXTL-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 239000004840 adhesive resin Substances 0.000 description 1
- 229920006223 adhesive resin Polymers 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000005119 alkyl cycloalkyl group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 235000006708 antioxidants Nutrition 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 101150059062 apln gene Proteins 0.000 description 1
- 125000001204 arachidyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 229920006378 biaxially oriented polypropylene Polymers 0.000 description 1
- 239000011127 biaxially oriented polypropylene Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 239000002981 blocking agent Substances 0.000 description 1
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 1
- 125000000068 chlorophenyl group Chemical group 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000000596 cyclohexenyl group Chemical group C1(=CCCCC1)* 0.000 description 1
- 125000000640 cyclooctyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000004715 ethylene vinyl alcohol Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 125000006038 hexenyl group Chemical group 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 125000002960 margaryl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 238000005649 metathesis reaction Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000001196 nonadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- SJYNFBVQFBRSIB-UHFFFAOYSA-N norbornadiene Chemical compound C1=CC2C=CC1C2 SJYNFBVQFBRSIB-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002958 pentadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
- B32B27/325—Layered products comprising a layer of synthetic resin comprising polyolefins comprising polycycloolefins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
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Description
本発明は、低分子量の有機化合物に対する非吸着性およびバリア性に優れ、かつ安定したヒートシールが可能なシーラント用樹脂組成物、積層フィルムおよび包装袋に関する。
本願は、２０１２年１月１１日に、日本に出願された特願２０１２−００３２２１号に基づき優先権を主張し、その内容をここに援用する。The present invention relates to a resin composition for a sealant, a laminated film, and a packaging bag, which are excellent in non-adsorption property and barrier property for a low molecular weight organic compound and are capable of stable heat sealing.
This application claims priority on January 11, 2012 based on Japanese Patent Application No. 2012-003221 for which it applied to Japan, and uses the content here.
従来のポリオレフィン系樹脂をシーラントとした包装フィルムは低分子量の有機化合物に対する非吸着性およびバリア性が劣り、飲食物や化粧品等の香気成分が吸着して風味が変化したり、化粧品や薬剤等の微量な有効成分が浸透あるいは吸着して効能が低下したりする欠点がある。また、包装フィルムに対する影響としては、内容品に含まれる香味成分やアルコール類、界面活性剤などの有機成分が浸透することにより、包装フィルム内部の接着剤層やアンカー剤層、印刷層等に悪影響を及ぼして層間のラミネート強度を低下させ、デラミネーション（剥離）を起こすおそれがあるという問題もある。 Conventional packaging films using polyolefin resin as a sealant are inferior in non-adsorbing property and barrier property to low molecular weight organic compounds, adsorbing flavor components such as food and drink, cosmetics, etc. There is a drawback that a small amount of an active ingredient permeates or adsorbs to lower the efficacy. Also, as an effect on the packaging film, organic components such as flavor components, alcohols, and surfactants contained in the contents permeate, and adversely affect the adhesive layer, anchor agent layer, printing layer, etc. inside the packaging film. There is also a problem that the lamination strength between the layers may be reduced to cause delamination.
特許文献１には、シクロオレフィンコポリマー（ＣＯＣ）を特定のエチレン−α−オレフィン共重合体にブレンドした樹脂組成物が記載されている。
特許文献２には、ガラス転移点の低い環状オレフィン系樹脂（Ａ）と、ガラス転移点の高い環状オレフィン系樹脂（Ｂ）とを、特定の配合割合範囲でブレンドした溶融押出用環状オレフィン系樹脂組成物が記載されている。Patent Document 1 describes a resin composition in which a cycloolefin copolymer (COC) is blended with a specific ethylene-α-olefin copolymer.
Patent Document 2 discloses a cyclic olefin resin for melt extrusion in which a cyclic olefin resin (A) having a low glass transition point and a cyclic olefin resin (B) having a high glass transition point are blended in a specific blending ratio range. A composition is described.
特許文献１の場合、エチレン−α−オレフィン共重合体がベース樹脂（主成分となる樹脂）であるため、包装フィルムを袋としたときに内容物に含まれる上記有機成分がシーラントに吸着しやすいという問題がある。
特許文献２の場合、実施例で用いられるものはＴＯＰＡＳ（登録商標）社のシクロオレフィンコポリマー（ＣＯＣ）同士をブレンドするものであり、包装フィルムを袋としたときに内容物に含まれる上記有機成分がシーラントに吸着しやすいという問題がある。In the case of Patent Document 1, since the ethylene-α-olefin copolymer is a base resin (resin that is a main component), the organic component contained in the contents is easily adsorbed to the sealant when the packaging film is used as a bag. There is a problem.
In the case of Patent Document 2, what is used in the example is a blend of TOPAS (registered trademark) cycloolefin copolymer (COC), and the organic component contained in the contents when the packaging film is used as a bag. Has a problem that it is easily adsorbed to the sealant.
本発明は、上記事情に鑑みてなされたものであり、内容物に含まれる有機成分に対する非吸着性と、ヒートシールとを向上することが可能なシーラント用樹脂組成物、積層フィルムおよび包装袋を提供することを課題とする。 The present invention has been made in view of the above circumstances, and provides a resin composition for a sealant, a laminated film, and a packaging bag capable of improving non-adsorption to an organic component contained in contents and heat sealing. The issue is to provide.
前記課題を解決するため、シクロオレフィンポリマー（以下、ＣＯＰと略記することがある）とシクロオレフィンコポリマー（以下、ＣＯＣと略記することがある）とを含有するシーラント用樹脂組成物であって、シクロオレフィンポリマーとシクロオレフィンコポリマーとの合計量が１００重量％であり、シクロオレフィンポリマー１０〜９５重量％と、シクロオレフィンコポリマー５〜９０重量％とを含有することを特徴とするシーラント用樹脂組成物を提供する。
また、本発明は、シクロオレフィンポリマーとシクロオレフィンコポリマーと添加剤とからなるシーラント用樹脂組成物であって、シクロオレフィンポリマーとシクロオレフィンコポリマーとの合計量を１００重量部として、シクロオレフィンポリマーが１０〜９５重量部、シクロオレフィンコポリマーが５〜９０重量部の配合比であることを特徴とするシーラント用樹脂組成物を提供する。
前記シクロオレフィンポリマーは、ノルボルネン骨格を有する環状オレフィンの重合体またはその水素添加物であり、前記シクロオレフィンコポリマーは、ノルボルネン骨格を有する環状オレフィンと非環状オレフィンとの重合体またはその水素添加物であることが好ましい。
また、本発明は、基材と、積層フィルムの一方の最表面となるシーラント層とを含む複数の層を有する積層フィルムにおいて、前記シーラント層が、前記シーラント用樹脂組成物を含有することを特徴とする積層フィルムを提供する。
また、本発明は、前記積層フィルムからなり、前記シーラント層をヒートシールしてなるヒートシール部を有することを特徴とする包装袋を提供する。
In order to solve the above-mentioned problem, a sealant resin composition comprising a cycloolefin polymer (hereinafter abbreviated as COP) and a cycloolefin copolymer (hereinafter abbreviated as COC), A sealant resin composition characterized in that the total amount of an olefin polymer and a cycloolefin copolymer is 100% by weight, and contains 10 to 95% by weight of a cycloolefin polymer and 5 to 90% by weight of a cycloolefin copolymer. provide.
The present invention also provides a resin composition for a sealant comprising a cycloolefin polymer, a cycloolefin copolymer and an additive, wherein the total amount of the cycloolefin polymer and the cycloolefin copolymer is 100 parts by weight, and the cycloolefin polymer is 10 parts by weight. Provided is a resin composition for a sealant, which is -95 parts by weight and the compounding ratio of the cycloolefin copolymer is 5 to 90 parts by weight.
The cycloolefin polymer is a polymer of a cyclic olefin having a norbornene skeleton or a hydrogenated product thereof, and the cycloolefin copolymer is a polymer of a cyclic olefin having a norbornene skeleton and an acyclic olefin or a hydrogenated product thereof. It is preferable .
Further, the present invention is a laminated film having a plurality of layers including a base material and a sealant layer that is one outermost surface of the laminated film, wherein the sealant layer contains the resin composition for sealant. A laminated film is provided.
Moreover, this invention provides the packaging bag characterized by having the heat seal part which consists of the said laminated | multilayer film and heat seals the said sealant layer.
本発明によれば、内容物に含まれる有機成分に対する非吸着性と、ヒートシール性とを向上することが可能なシーラント用樹脂組成物、積層フィルムおよび包装袋を提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, the resin composition for sealants, laminated | multilayer film, and a packaging bag which can improve the non-adsorption with respect to the organic component contained in the content, and heat sealability can be provided.
以下、好適な実施形態に基づき、本発明を説明する。
本形態例のシーラント用樹脂組成物は、シクロオレフィンポリマー（ＣＯＰ）とシクロオレフィンコポリマー（ＣＯＣ）とを含有するシーラント用樹脂組成物であって、ＣＯＰ１０〜９５重量％と、ＣＯＣ５〜９０重量％とを含有する。Hereinafter, the present invention will be described based on preferred embodiments.
The sealant resin composition of the present embodiment is a sealant resin composition containing a cycloolefin polymer (COP) and a cycloolefin copolymer (COC), and has a COP of 10 to 95% by weight, a COC of 5 to 90% by weight, Containing.
また、本形態例の積層フィルムは、基材とシーラント層と、必要に応じて他の中間層とを積層した構成である。すなわち、積層フィルムの一方の最表面となるシーラント層と基材と、必要に応じて他の中間層、接着剤層またはアンカー剤層などとの複数の層を有する。
ここで、シーラント層とは、ヒートシールに用いられる層であり、包装材料としては内容品に接する最内層に配置されるものである。該シーラント層が、本形態例のシーラント用樹脂組成物で形成されている。
基材または他の中間層と、シーラント層との積層は、接着剤層又はアンカー剤層を介しても良いし、基材に直接積層されていても良い。前記中間層としては、補強層、ガスバリア層、遮光層、印刷層など、適宜、一層または複数層を選択することができる。Moreover, the laminated film of the present embodiment has a configuration in which a base material, a sealant layer, and another intermediate layer as necessary are laminated. That is, it has a plurality of layers including a sealant layer that is one of the outermost surfaces of the laminated film, a base material, and another intermediate layer, an adhesive layer, an anchor agent layer, or the like as necessary.
Here, the sealant layer is a layer used for heat sealing, and is disposed in the innermost layer in contact with the contents as a packaging material. The sealant layer is formed of the resin composition for sealant of this embodiment.
The base material or other intermediate layer and the sealant layer may be laminated via an adhesive layer or an anchor agent layer, or may be directly laminated on the base material. As the intermediate layer, one or more layers such as a reinforcing layer, a gas barrier layer, a light-shielding layer, and a printing layer can be appropriately selected.
本発明のシーラント用樹脂組成物に用いられるシクロオレフィンポリマーは、例えば環状オレフィンの単独重合体もしくは２種以上の環状オレフィンの共重合体またはその水素添加物であり、通常ＣＯＰ（Ｃｙｃｌｏｏｌｅｆｉｎ ｐｏｌｙｍｅｒ）と称されるものである。前記ＣＯＰは、好ましくは非結晶性の重合体であり、より好ましくは、メタセシス等による環状オレフィンの開環重合体またはその水素添加物である。前記ＣＯＰは、ＣＯＣ等に比べて脂環式構造を含有する比率が高く、非吸着性に優れるため、好ましい。
例えば、ＣＯＰは以下の化学式（１）で表される構造を有する。The cycloolefin polymer used in the resin composition for a sealant of the present invention is, for example, a homopolymer of a cyclic olefin, a copolymer of two or more cyclic olefins, or a hydrogenated product thereof, and is usually referred to as COP (Cycloolefin polymer). It is what is done. The COP is preferably an amorphous polymer, more preferably a ring-opening polymer of a cyclic olefin by metathesis or the like or a hydrogenated product thereof. The COP is preferable because it has a higher ratio of containing an alicyclic structure than COC or the like and is excellent in non-adsorption.
For example, COP has a structure represented by the following chemical formula (1).
（式中、Ｒ１およびＲ２は互いに同一または異種の炭素数１〜２０の有機基または水素原子を示し、また、Ｒ１とＲ２は互いに環を形成していてもよい。ｎは１以上の整数を示す。）(Wherein R 1 and R 2 represent the same or different organic group having 1 to 20 carbon atoms or a hydrogen atom, and R 1 and R 2 may form a ring with each other; n is 1; Indicates the integer above.)
本発明のシーラント用樹脂組成物に用いられるシクロオレフィンコポリマーは、例えば１種もしくは２種以上の環状オレフィンと１種もしくは２種以上の非環状オレフィンとの共重合体またはその水素添加物であり、通常ＣＯＣ（Ｃｙｃｌｏｏｌｅｆｉｎ ｃｏｐｏｌｙｍｅｒ）と称されるものである。前記ＣＯＣは、好ましくは非結晶性の重合体であり、より好ましくは、環状オレフィンとエチレンとの共重合体またはその水素添加物である。
例えば、ＣＯＣは下記化学式（２）で表される構造を有することができる。The cycloolefin copolymer used in the resin composition for sealant of the present invention is, for example, a copolymer of one or two or more cyclic olefins and one or two or more acyclic olefins or a hydrogenated product thereof, Usually, it is called COC (Cyclorefin copolymer). The COC is preferably an amorphous polymer, more preferably a copolymer of a cyclic olefin and ethylene or a hydrogenated product thereof.
For example, COC can have a structure represented by the following chemical formula (2).
（式中、Ｒ１およびＲ２は互いに同一または異種の炭素数１〜２０の有機基または水素原子を示し、また、Ｒ１とＲ２は互いに環を形成していてもよい。Ｒ３は炭素数１〜２０の有機基または水素原子を示す。ｍおよびｐはそれぞれ１以上の整数を示す。）(Wherein R 1 and R 2 represent the same or different organic group having 1 to 20 carbon atoms or a hydrogen atom, and R 1 and R 2 may form a ring with each other. R 3 represents An organic group having 1 to 20 carbon atoms or a hydrogen atom, and m and p each represent an integer of 1 or more.)
上記炭素数１〜２０の有機基として、より具体的には、例えばメチル、エチル、ｎ−プロピル、ｉ−プロピル、ｎ−ブチル、ｉ−ブチル、ｓｅｃ−ブチル、ｔ−ブチル、ｉ−ペンチル、ｔ−ペンチル、ｎ−ヘキシル、ｎ−ヘプチル、ｎ−オクチル、ｔ−オクチル（１，１−ジメチル−３，３−ジメチルブチル）、２−エチルヘキシル、ノニル、デシル、ウンデシル、ドデシル、トリデシル、テトラデシル、ペンタデシル、ヘキサデシル、ヘプタデシル、オクタデシル、ノナデシル、イコシル等のアルキル基；シクロペンチル、シクロヘキシル、シクロヘプチル、シクロオクチル等のシクロアルキル基；１−メチルシクロペンチル、１−メチルシクロヘキシル、１−メチル−４−ｉ−プロピルシクロヘキシル等のアルキルシクロアルキル基；アリル、プロペニル、ブテニル、２−ブテニル、ヘキセニル、シクロヘキセニル等のアルケニル基；フェニル基、ナフチル基、メチルフェニル基、メトキシフェニル基、ビフェニル基、フェノキシフェニル基、クロロフェニル基、スルホフェニル基等のアリール基；ベンジル基、２−フェニルエチル基（フェネチル基）、α−メチルベンジル基、α，α−ジメチルベンジル基等のアラルキル基等を挙げることができるが、これらに限定されるものではない。また、これらは１種を単独で、あるいは２種以上を併用しても良い。 More specifically, examples of the organic group having 1 to 20 carbon atoms include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, t-butyl, i-pentyl, t-pentyl, n-hexyl, n-heptyl, n-octyl, t-octyl (1,1-dimethyl-3,3-dimethylbutyl), 2-ethylhexyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, Alkyl groups such as pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, icosyl; cycloalkyl groups such as cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl; 1-methylcyclopentyl, 1-methylcyclohexyl, 1-methyl-4-i-propyl Alkylcycloalkyl groups such as cyclohexyl; Alkenyl groups such as phenyl, propenyl, butenyl, 2-butenyl, hexenyl, cyclohexenyl; aryl groups such as phenyl, naphthyl, methylphenyl, methoxyphenyl, biphenyl, phenoxyphenyl, chlorophenyl, and sulfophenyl An aralkyl group such as a benzyl group, a 2-phenylethyl group (phenethyl group), an α-methylbenzyl group, an α, α-dimethylbenzyl group, and the like, but is not limited thereto. These may be used alone or in combination of two or more.
前記ＣＯＰおよび前記ＣＯＣの構成モノマーとして使用される環状オレフィンとしては、例えば、炭素原子数が３〜２０のシクロアルカンを有するビニルシクロアルカンおよびその誘導体、炭素原子数が３〜２０のモノシクロアルケンおよびその誘導体、またはノルボルネン骨格を有する環状オレフィン（ノルボルネン系モノマー）が好ましい。
ノルボルネン系モノマーとしては、例えば、下記化学式（３）に示すように、ビシクロ［２．２．１］−２−ヘプテン（ノルボルネン）およびその誘導体、トリシクロ［４．３．０．１2,5］−３−デセンおよびその誘導体、テトラシクロ［４．４．０．１2,5．１7,10］−３−ドデセンおよびその誘導体、ペンタシクロ［６．５．１．１3,6．０2,7．０9,13］−４−ペンタデセンおよびその誘導体、ペンタシクロ［７．４．０．１2,5．１9,12．０8,13］−３−ペンタデセンおよびその誘導体、ペンタシクロ［８．４．０．１2,5．１9,12．０8,13］−３−ヘキサデセンおよびその誘導体、ペンタシクロ［６．６．１．１3,6．０2,7．０9,14］−４−ヘキサデセンおよびその誘導体、ヘキサシクロ［６．６．１．１3,6．１10,13．０2,7．０9,14］−４−ヘプタデセンおよびその誘導体、ヘプタシクロ［８．７．０．１2,9．１4,7．１11,17．０3,8．０12,16］−５−エイコセンおよびその誘導体、ヘプタシクロ［８．７．０．１3,6．１10,17．１12,15．０2,7．０11,16］−４−エイコセンおよびその誘導体、ヘプタシクロ［８．８．０．１2,9．１4,7．１11,18．０3,8．０12,17］−５−ヘンエイコセンおよびその誘導体、オクタシクロ［８．８．０．１2,9．１4,7．１11,18．１13,16．０3,8．０12,17］−５−ドコセンおよびその誘導体、ノナシクロ［１０．９．１．１4,7．１13,20．１15,18．０2,10．０3,8．０12,21．０14,19］−５−ペンタコセンおよびその誘導体等が挙げられる。誘導体としては、置換基として上記炭素数１〜２０の有機基（Ｒ１、Ｒ２）を１つまたは２つ以上有するものや、ノルボルナジエンのように不飽和結合を２以上有するもの等が挙げられる。Examples of the cyclic olefin used as a constituent monomer of the COP and the COC include, for example, vinylcycloalkanes having 3 to 20 carbon atoms and derivatives thereof, monocycloalkenes having 3 to 20 carbon atoms, and A derivative thereof or a cyclic olefin having a norbornene skeleton (norbornene monomer) is preferred.
Examples of the norbornene-based monomer include bicyclo [2.2.1] -2-heptene (norbornene) and its derivatives, tricyclo [4.3.0.1 2,5 ] as shown in the following chemical formula (3). -3-decene and its derivatives, tetracyclo [4.4.0.1 2,5 . 1 7,10 ] -3-dodecene and its derivatives, pentacyclo [6.5.1.1 3,6 . 0 2,7 . 0 9,13] -4-pentadecene and its derivatives, pentacyclo [7.4.0.1 2,5. 1 9,12 . 0 8,13] -3-pentadecene and its derivatives, pentacyclo [8.4.0.1 2,5. 1 9,12 . 0 8,13] -3-hexadecene and derivatives thereof, pentacyclo [6.6.1.1 3, 6. 0 2,7 . 0 9,14] -4-hexadecene and derivatives thereof, hexacyclo [6.6.1.1 3, 6. 1 10,13 . 0 2,7 . 0 9,14] -4-heptadecene and its derivatives, heptacyclo [8.7.0.1 2,9. 1 4,7 . 1 11,17 . 0 3,8 . 0 12,16 ] -5-eicosene and its derivatives, heptacyclo [8.7.0.1 3,6 . 1 10,17 . 1 12,15 . 0 2,7 . 0 11,16 ] -4-eicosene and its derivatives, heptacyclo [8.8.0.1 2,9 . 1 4,7 . 1 11,18 . 0 3,8 . 0 12,17 ] -5- heneicosene and its derivatives, octacyclo [8.8.0.1 2,9 . 1 4,7 . 1 11,18 . 1 13,16 . 0 3,8 . 0 12,17 ] -5-docosene and derivatives thereof, nonacyclo [10.9.1.1 4,7 . 1 13,20 . 1 15,18 . 0 2,10 . 0 3,8 . 0 12,21 . 0 14,19] -5-pentacosene and derivatives thereof. Examples of the derivative include those having one or two or more organic groups having 1 to 20 carbon atoms (R 1 , R 2 ) as substituents, and those having two or more unsaturated bonds such as norbornadiene. .
前記ＣＯＣの構成モノマーとして使用される非環状オレフィンとしては、例えば、エチレンや、プロピレン、１−ブテン、１−ペンテン、１−ヘキセン、１−ヘプテン、１−オクテン等のα−オレフィン、３−デセンや３−ドデセン等が挙げられる。 Examples of the acyclic olefin used as a constituent monomer of the COC include ethylene, α-olefins such as propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, and 3-decene. And 3-dodecene.
前記ＣＯＰは、ノルボルネン骨格を有する環状オレフィンの重合体またはその水素添加物であることが好ましく、前記ＣＯＣは、ノルボルネン骨格を有する環状オレフィンと非環状オレフィンとの重合体またはその水素添加物であることが好ましい。
ＣＯＰとしては市販品を用いることができ、例えば日本ゼオン株式会社製のゼオネックス、ゼオノアを好適に用いることができる。ＣＯＣとしても市販品を用いることができ、例えば三井化学株式会社製のアペル、ポリプラスチックス株式会社製のＴＯＰＡＳを好適に用いることができる。The COP is preferably a polymer of a cyclic olefin having a norbornene skeleton or a hydrogenated product thereof, and the COC is a polymer of a cyclic olefin having a norbornene skeleton and an acyclic olefin or a hydrogenated product thereof. Is preferred.
A commercial item can be used as COP, for example, ZEONEX and ZEONOR made by ZEON CORPORATION can be suitably used. Commercially available products can also be used as the COC, for example, Appel manufactured by Mitsui Chemicals, Inc., and TOPAS manufactured by Polyplastics Co., Ltd. can be preferably used.
本発明の積層フィルムで用いられるシーラント層は、前記シーラント用樹脂組成物を用いて形成されている。該樹脂組成物は、本発明の目的を損なわない範囲で、適宜の添加剤を添加することができる。添加剤としては、例えば酸化防止剤、滑剤、アンチブロッキング剤、難燃剤、紫外線吸収剤、光安定剤、帯電防止剤、着色剤等が挙げられる。
前記シーラント用樹脂組成物のガラス転移温度（Ｔｇ）は、４０℃より高いことが好ましい。ガラス転移温度が４０℃以下の場合、得られるシーラント層の非吸着性が低下する。また、ブレンド前のＣＯＰのＴｇが５０〜１４０℃であることが好ましく、ＣＯＣのＴｇも５０〜１４０℃であることが好ましい。The sealant layer used in the laminated film of the present invention is formed using the sealant resin composition. An appropriate additive can be added to the resin composition as long as the object of the present invention is not impaired. Examples of the additive include an antioxidant, a lubricant, an anti-blocking agent, a flame retardant, an ultraviolet absorber, a light stabilizer, an antistatic agent, and a colorant.
The glass transition temperature (Tg) of the resin composition for sealant is preferably higher than 40 ° C. When the glass transition temperature is 40 ° C. or lower, the non-adsorbability of the resulting sealant layer is lowered. Moreover, it is preferable that Tg of COP before blending is 50-140 degreeC, and it is preferable that Tg of COC is also 50-140 degreeC.
本発明においては、ＣＯＰとＣＯＣとの配合比は、両者の合計を１００重量％として、ＣＯＰ１０〜９５重量％、ＣＯＣ５〜９０重量％である。これにより、非吸着性は優れるがシール強度は低いＣＯＰと、シール強度は優れるが非吸着性はＣＯＰよりも低いＣＯＣとに比べて、シール強度および非吸着性が共に良好なシーラント材が得られる。また、上記配合比とすることで、ＣＯＰやＣＯＣが単独である場合に比べて、引張伸度が著しく向上するという、驚くべき効果を確認することができた。引張伸度は、値が大きいほどフィルムが伸びやすく柔軟であることを意味する。 In the present invention, the compounding ratio of COP and COC is 10 to 95% by weight of COP and 5 to 90% by weight of COC, where the total of both is 100% by weight. As a result, a sealant material having both excellent sealing strength and non-adsorbing property can be obtained as compared with COP having excellent non-adsorbing property but low sealing strength and COC having excellent sealing strength but non-adsorbing property lower than COP. . Moreover, the surprising effect that the tensile elongation is remarkably improved as compared with the case where COP and COC were used alone could be confirmed by setting the above blend ratio. The tensile elongation means that the larger the value is, the more easily the film is stretched and flexible.
積層フィルムの基材としては、耐熱性や強度などの機械的特性、印刷適性に優れた延伸フィルムが好ましく、具体的には、２軸延伸ポリエチレンテレフタレート（Ｏ−ＰＥＴ）フィルム、２軸延伸ナイロン（Ｏ−Ｎｙ）フィルム、２軸延伸ポリプロピレン（ＯＰＰ）フィルム等を挙げることができる。前記基材の厚さは通常１０〜５０μｍであり、好ましくは１０〜３０μｍである。 As the base material of the laminated film, a stretched film excellent in mechanical properties such as heat resistance and strength and printability is preferable. Specifically, a biaxially stretched polyethylene terephthalate (O-PET) film, a biaxially stretched nylon ( O-Ny) film, biaxially oriented polypropylene (OPP) film, and the like. The thickness of the substrate is usually 10 to 50 μm, preferably 10 to 30 μm.
シーラント層の内側には、シーラント層を基材または他のフィルムと接着するため、アンカー剤層または接着剤層が介在されることが好ましい。シーラント層を押出ラミネート法で形成する場合には、シーラント層の内側に接するアンカー剤層が形成される。基材としてＯ−ＰＥＴを用いる場合にはアンカー剤層を用いなくとも良い。予め単層フィルムとして作製したシーラント層をドライラミネート法によって基材または他のフィルムと接着する場合には、シーラント層の内側に接する接着剤層が形成される。また、共押出法を用いる場合は酸変性ポリオレフィンなどの接着性樹脂を用いても良い。
前記アンカー剤層を構成するアンカー剤としては、ポリウレタン系、ポリエーテル系、アルキルチタネート（有機チタン化合物）系等、一般的に押出ラミネート法に使用されるアンカー剤が使用でき、積層フィルムの用途に合わせて選択可能である。
前記接着剤層を構成する接着剤としては、ポリウレタン系、ポリエーテル系等、一般的にドライラミネート法に使用される接着剤を使用でき、積層フィルムの用途に合わせて選択可能である。An anchor agent layer or an adhesive layer is preferably interposed inside the sealant layer in order to adhere the sealant layer to a substrate or other film. When the sealant layer is formed by an extrusion laminating method, an anchor agent layer in contact with the inside of the sealant layer is formed. When O-PET is used as the substrate, the anchor agent layer need not be used. In the case where a sealant layer prepared in advance as a single layer film is bonded to a substrate or another film by a dry lamination method, an adhesive layer in contact with the inside of the sealant layer is formed. In the case of using the coextrusion method, an adhesive resin such as acid-modified polyolefin may be used.
As an anchoring agent constituting the anchoring agent layer, an anchoring agent generally used for extrusion laminating methods such as polyurethane, polyether, alkyl titanate (organic titanium compound), etc. can be used. They can be selected together.
As an adhesive which comprises the said adhesive bond layer, the adhesive agent generally used for dry lamination methods, such as a polyurethane type and a polyether type | system | group, can be used, and it can select according to the use of a laminated | multilayer film.
前記シーラント層の内側のアンカー剤層または接着剤層と前記基材との間には、中間層としてガスバリア層や補強層などが存在していても構わない。
補強層は積層フィルムの強度特性を補完する役割であって、補強層を構成する樹脂としては、ポリプロピレン（ＰＰ）、ポリエチレン（ＰＥ）等のポリオレフィン系樹脂、２軸延伸ポリエチレンテレフタレート（Ｏ−ＰＥＴ）、２軸延伸ナイロン（Ｏ−Ｎｙ）、２軸延伸ポリプロピレン（ＯＰＰ）等を挙げることができる。補強層の厚みは、通常５〜５０μｍであり、好ましくは１０〜３０μｍである。Between the anchor agent layer or adhesive layer inside the sealant layer and the base material, a gas barrier layer, a reinforcing layer, or the like may exist as an intermediate layer.
The reinforcing layer has a role of complementing the strength characteristics of the laminated film. The resin constituting the reinforcing layer is a polyolefin resin such as polypropylene (PP) or polyethylene (PE), biaxially stretched polyethylene terephthalate (O-PET). Biaxially stretched nylon (O-Ny), biaxially stretched polypropylene (OPP), etc. can be mentioned. The thickness of a reinforcement layer is 5-50 micrometers normally, Preferably it is 10-30 micrometers.
ガスバリア層は、酸素や水蒸気等のガスが積層フィルムを透過することを遮断するためガスバリア性を付与する機能を有する。このようなガスバリア層としては、金属箔、アルミニウムや無機酸化物の蒸着層、エチレン−ビニルアルコール共重合体（ＥＶＯＨ）、塩化ビニリデン等のガスバリア性樹脂層が挙げられる。なお、バリア層を補強層として共用しても構わない。これらのガスバリア層は、基材または補強層を構成するフィルムの片面に設けることができ、一般には基材とシーラント層との間の中間層として設けられる。無機酸化物蒸着層の場合は、基材よりも外側の最外層（積層フィルムにおいてシーラント層の反対側の最表層）としても利用できる。
ガスバリア層の厚みは、金属箔またはガスバリア性樹脂層による場合は通常５〜５０μｍであり、好ましくは１０〜３０μｍである。ガスバリア層として金属蒸着層または無機酸化物蒸着層を用いる場合には、これより薄くすることができる。The gas barrier layer has a function of imparting gas barrier properties to block gas such as oxygen and water vapor from passing through the laminated film. Examples of such a gas barrier layer include a metal foil, a vapor deposition layer of aluminum or an inorganic oxide, a gas barrier resin layer such as ethylene-vinyl alcohol copolymer (EVOH), or vinylidene chloride. In addition, you may share a barrier layer as a reinforcement layer. These gas barrier layers can be provided on one side of the film constituting the base material or the reinforcing layer, and are generally provided as an intermediate layer between the base material and the sealant layer. In the case of an inorganic oxide vapor deposition layer, it can also be used as the outermost layer outside the substrate (the outermost layer on the opposite side of the sealant layer in the laminated film).
The thickness of the gas barrier layer is usually 5 to 50 μm, preferably 10 to 30 μm, when using a metal foil or a gas barrier resin layer. When using a metal vapor deposition layer or an inorganic oxide vapor deposition layer as a gas barrier layer, it can be made thinner than this.
本発明の積層フィルムを製造する方法としては、特に限定されることなく、押出ラミネート法、ドライラミネート法、共押出法またはこれらの併用により、積層フィルムを構成する各層を適宜積層すればよい。
本形態例の積層フィルムにおいて、シーラント層の厚さは、包装材料の用途にも依存し、特に限定されるものではないが、通常は５〜１５０μｍ程度であり、好ましくは１５〜８０μｍである。The method for producing the laminated film of the present invention is not particularly limited, and each layer constituting the laminated film may be appropriately laminated by an extrusion lamination method, a dry lamination method, a co-extrusion method, or a combination thereof.
In the laminated film of this embodiment, the thickness of the sealant layer depends on the use of the packaging material and is not particularly limited, but is usually about 5 to 150 μm, preferably 15 to 80 μm.
本形態例の積層フィルムは、ヒートシール性と加工適性とがともに優れるので、通常の製袋機や製袋充填機を用いた製袋に適している。
本形態例の包装袋は、上述の積層フィルムの前記シーラント層をヒートシールして得られる。本形態例の包装袋は、低分子量成分の非吸着性およびバリア性にも優れているから、飲食物や化粧品、薬剤等の包装袋として好適に利用できる。包装袋の形態は、三方袋、四方袋、合掌貼り袋、ガゼット袋、自立袋等の包装袋（パウチ）のほか、例えばバッグインボックス用の内袋やドラム缶内装袋などの大型の袋等、特に限定なく適用可能である。Since the laminated film of this embodiment is excellent in both heat sealability and processability, it is suitable for bag making using an ordinary bag making machine or bag making filling machine.
The packaging bag of this embodiment is obtained by heat-sealing the sealant layer of the above laminated film. Since the packaging bag of this embodiment is excellent in the non-adsorption property and the barrier property of low molecular weight components, it can be suitably used as a packaging bag for foods, drinks, cosmetics, drugs, and the like. The form of the packaging bag includes three-sided bags, four-sided bags, joint-laminated bags, gusset bags, self-standing bags and other packaging bags (pouches), for example, large bags such as inner bags for bag-in-boxes and drum can interior bags, It is applicable without particular limitation.
本発明の包装袋に注出口を設ける場合、包装袋を構成する積層フィルムのシーラント層と接合して密封性が確保できればどのような注出口でも好適に使用できるが、前記積層フィルムのシーラント層にヒートシール可能な樹脂で注出口を形成し、この注出口と積層フィルムとをヒートシールによって接合することがより好ましい。積層フィルムと注出口とをヒートシールする場合、シーラント層を内側として積層フィルムを重ね合わせた間に注出口を挿入してヒートシールしてもよいし、注出口の一端にフランジ部や舟形形状の融着基部を設け、このフランジ部や融着基部を積層フィルムに設けた穴の周縁や包装袋の開口部内面にヒートシールしてもよい。 When the spout is provided in the packaging bag of the present invention, any spout can be suitably used as long as the sealing film can be secured by joining with the sealant layer of the laminated film constituting the packaging bag. More preferably, the spout is formed of a heat-sealable resin, and the spout and the laminated film are joined by heat sealing. When heat-sealing the laminated film and the spout, the spout may be inserted and heat-sealed while the laminated film is overlapped with the sealant layer on the inside. A fusion base portion may be provided, and the flange portion or the fusion base portion may be heat sealed to the peripheral edge of the hole provided in the laminated film or the inner surface of the opening of the packaging bag.
以下、実施例をもって本発明を具体的に説明する。 Hereinafter, the present invention will be specifically described with reference to examples.
（シーラント材）
表１および表２に示すように、ＣＯＰを１００〜０重量％、ＣＯＣを０〜１００重量％の範囲で配合した組成により、シーラント材用樹脂組成物を製造した。次いで、得られたシーラント材用樹脂組成物を溶融混練後、押出成形により、所定の厚さのフィルム状に成形する方法によりシーラント材を製造した。
なお、用いたＣＯＰおよびＣＯＣは、次のとおりである。
「ＣＯＰ」・・・シクロオレフィンポリマー（日本ゼオン株式会社製、商品名ＺＥＯＮＯＲ（登録商標）１０２０Ｒ）
「ＣＯＣ１」・・・シクロオレフィンコポリマー（ポリプラスチックス株式会社製、商品名ＴＯＰＡＳ（登録商標）８００７Ｆ−０４）
「ＣＯＣ２」・・・シクロオレフィンコポリマー（三井化学株式会社製、商品名アペル（登録商標）ＡＰＬ８００８Ｔ）(Sealant material)
As shown in Tables 1 and 2, a resin composition for a sealant material was produced with a composition in which COP was blended in an amount of 100 to 0% by weight and COC in a range of 0 to 100% by weight. Next, after the obtained resin composition for sealant material was melt-kneaded, a sealant material was produced by extrusion molding into a film having a predetermined thickness.
The COP and COC used are as follows.
“COP”: cycloolefin polymer (manufactured by ZEON CORPORATION, trade name ZEONOR (registered trademark) 1020R)
"COC1" ... cycloolefin copolymer (manufactured by Polyplastics Co., Ltd., trade name TOPAS (registered trademark) 8007F-04)
"COC2" ... cycloolefin copolymer (Mitsui Chemicals, trade name: Apel (registered trademark) APL8008T)
（積層フィルムの製造）
厚み３０μｍのシーラント材とＰＥＴフィルムおよびＡｌ箔とをドライラミネートにより貼り合わせ、ＰＥＴ１２μｍ／Ａｌ箔９μｍ／シーラント材３０μｍの層構成を有する積層フィルムを得た。(Manufacture of laminated film)
A 30 μm-thick sealant material, a PET film, and an Al foil were bonded together by dry lamination to obtain a laminated film having a layer configuration of PET 12 μm / Al foil 9 μm / sealant material 30 μm.
（評価方法）
上記積層フィルムを用いてパウチを作製し、下記に説明する評価を行った。ただし（４）の引張特性は、シーラント材から作製した試験片を評価した。(Evaluation method)
A pouch was produced using the laminated film and evaluated as described below. However, the tensile property of (4) evaluated the test piece produced from the sealant material.
（１）ヒートシール強度
ＪＩＳ Ｚ ０２３８に準じて、パウチのヒートシール部のシール強度（Ｎ／１５ｍｍ）を引張速度３００ｍｍ／ｍｉｎ、幅１５ｍｍにて測定した。ヒートシール条件は、１４０℃、１６０℃、１８０℃、２００℃、２２０℃のうちのいずれかの温度において、圧力０．２ＭＰａで１秒間加熱および加圧するものである。(1) Heat seal strength According to JIS Z 0238, the seal strength (N / 15 mm) of the heat seal part of the pouch was measured at a tensile speed of 300 mm / min and a width of 15 mm. The heat sealing condition is to heat and pressurize at a pressure of 0.2 MPa for 1 second at any temperature among 140 ° C., 160 ° C., 180 ° C., 200 ° C., and 220 ° C.
（２）ヒートシール強度の安定領域
（１）で測定したヒートシール強度が１３Ｎ／ｍｍ以上であり、かつ、各溶着温度の前後２０℃のいずれかのシール強度が±１Ｎ／１５ｍｍ以内の範囲に収まる温度範囲を、安定領域と定義した。(2) Heat seal strength stability region The heat seal strength measured in (1) is 13 N / mm or more, and the seal strength at 20 ° C. before and after each welding temperature is within ± 1 N / 15 mm. The temperature range within which the temperature falls is defined as the stable region.
（３）酢酸α−トコフェロールの残存率
有効成分として酢酸α−トコフェロール（ビタミンＥアセテート）を含む市販の化粧水２．５ｍｌをパウチに入れ、パウチの開口部を圧力０．２ＭＰａ、時間１秒、温度１８０℃でヒートシールして密封した。密封したパウチを４０℃で１ヶ月ないし３ヶ月保管した後に開封し、化粧水中の酢酸α−トコフェロールの残存量を高速液体クロマトグラフィ法で定量し、前記残存量をもとに有効成分の残存率を算出した。(3) Residual rate of α-tocopherol acetate 2.5 ml of a commercially available lotion containing α-tocopherol acetate (vitamin E acetate) as an active ingredient is put in the pouch, and the opening of the pouch has a pressure of 0.2 MPa, a time of 1 second, It heat-sealed at the temperature of 180 degreeC, and sealed. The sealed pouch is opened for 1 to 3 months at 40 ° C. and then opened. The residual amount of α-tocopherol acetate in the lotion is quantified by high performance liquid chromatography, and the residual ratio of the active ingredient is determined based on the residual amount. Calculated.
（４）引張特性
シーラント材の引張強度（Ｎ／１５ｍｍ）及び引張伸度（％）は、ＪＩＳ Ｋ ７１２７「プラスチック−引張特性の試験方法」に規定された測定方法に準じて測定した。試験片の幅は１５ｍｍ、引張速度は３００ｍｍ／ｍｉｎとした。引張伸度の掴み具間は５０ｍｍとした。(4) Tensile properties The tensile strength (N / 15 mm) and tensile elongation (%) of the sealant material were measured in accordance with the measurement method defined in JIS K 7127 “Plastics—Test method for tensile properties”. The width of the test piece was 15 mm, and the tensile speed was 300 mm / min. The distance between the grips of the tensile elongation was 50 mm.
評価結果を表１から表４に示す。表１および表２の「ヒートシール強度」の欄において、「ヒートシール強度の安定領域」に含まれるものには、下線を添えた。 The evaluation results are shown in Tables 1 to 4. In the column of “Heat seal strength” in Tables 1 and 2, those included in the “stable region of heat seal strength” are underlined.
以上の結果より、ＣＯＰとＣＯＣとの配合比（樹脂組成物全体、すなわち、ＣＯＰとＣＯＣとの合計量を１００重量％とする。）が、ＣＯＰ１０〜９５重量％、ＣＯＣ５〜９０重量％である場合（例４〜８および例１２〜２１）には、シール強度、非吸着性に優れていた。また、ＣＯＰ単独（例１）やＣＯＣ単独（例１１および例２３）に比べて、引張伸度が著しく向上した。ＣＯＰ単独（例１）では、十分なヒートシール温度が得られる温度が２００℃以上と高温であり、シール強度の安定領域がみられなかった。
ＣＯＣ１が８０重量％以上（例９〜１１）では、引張伸度が低く、ＣＯＣ１単独（例１１）と同程度であった。さらに、ＣＯＣ１単独（例１１）では、１８０℃程度の低温ではヒートシール強度が良いが、それ以上の温度ではヒートシール強度が下降した。
ＣＯＣ２が９５重量％以上（例２２）では、ヒートシール強度および引張伸度が低く、ＣＯＣ２単独（例２３）と同程度かそれよりも低下した。From the above results, the blending ratio of COP and COC (the total resin composition, that is, the total amount of COP and COC is 100% by weight) is 10 to 95% by weight of COP and 5 to 90% by weight of COC. In cases (Examples 4 to 8 and Examples 12 to 21), the sealing strength and non-adsorption were excellent. Also, the tensile elongation was significantly improved as compared with COP alone (Example 1) and COC alone (Examples 11 and 23). With COP alone (Example 1), the temperature at which a sufficient heat seal temperature was obtained was as high as 200 ° C. or higher, and a stable region of seal strength was not observed.
When COC1 was 80% by weight or more (Examples 9 to 11), the tensile elongation was low, which was similar to that of COC1 alone (Example 11). Furthermore, with COC1 alone (Example 11), the heat seal strength was good at a low temperature of about 180 ° C., but the heat seal strength was lowered at a temperature higher than that.
When the COC2 was 95% by weight or more (Example 22), the heat seal strength and the tensile elongation were low, and were the same as or lower than those of the COC2 alone (Example 23).
本発明は、特に、飲食物や化粧品、薬剤等、香料や有効成分を含有する内容品の包装に好適に利用することができる。 Especially this invention can be utilized suitably for the packaging of the content goods containing a fragrance | flavor and an active ingredient, such as food and drink, cosmetics, and a medicine.
Claims (5)
前記シクロオレフィンコポリマーは、ノルボルネン骨格を有する環状オレフィンと非環状オレフィンとの重合体またはその水素添加物であることを特徴とする請求項１又は２に記載のシーラント用樹脂組成物。 The cycloolefin polymer is a polymer of cyclic olefin having a norbornene skeleton or a hydrogenated product thereof,
The resin composition for a sealant according to claim 1 or 2 , wherein the cycloolefin copolymer is a polymer of a cyclic olefin having a norbornene skeleton and an acyclic olefin or a hydrogenated product thereof.
前記シーラント層が、請求項１〜３のいずれか１項に記載のシーラント用樹脂組成物を含有することを特徴とする積層フィルム。 In a laminated film having a plurality of layers including a base material and a sealant layer that is one outermost surface of the laminated film,
The said sealant layer contains the resin composition for sealants of any one of Claims 1-3, The laminated | multilayer film characterized by the above-mentioned.
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| PCT/JP2013/050019 WO2013105524A1 (en) | 2012-01-11 | 2013-01-07 | Resin composition for sealants, laminated film, and packaging bag |
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| CN110126376A (en) | 2012-12-07 | 2019-08-16 | 比密斯公司 | Multilayer film |
| US20150225151A1 (en) | 2014-02-11 | 2015-08-13 | Christopher L. Osborn | Anti-Scalping Transdermal Patch Packaging Film |
| US9468584B2 (en) | 2014-04-02 | 2016-10-18 | Bemis Company, Inc. | Child-resistant packaging |
| JP6451987B2 (en) * | 2015-03-17 | 2019-01-16 | Dic株式会社 | Barrier laminate and packaging material using the same |
| JP6085639B2 (en) * | 2015-06-03 | 2017-02-22 | ポリプラスチックス株式会社 | Low adsorptive packaging bag |
| JP6993554B2 (en) * | 2016-04-18 | 2022-01-13 | キョーラク株式会社 | Laminated peeling container |
| WO2017183502A1 (en) * | 2016-04-18 | 2017-10-26 | キョーラク株式会社 | Peelable laminated container |
| WO2018016443A1 (en) * | 2016-07-20 | 2018-01-25 | 凸版印刷株式会社 | Sealant film, multilayer film using same and packaging bag |
| CN110300659A (en) * | 2017-02-15 | 2019-10-01 | 凸版印刷株式会社 | Laminated body and its manufacturing method, package body and packing article |
| EP3693162A4 (en) * | 2017-10-03 | 2021-06-16 | Toppan Printing Co., Ltd. | Laminated body, package, and packaging article |
| JP6987002B2 (en) * | 2018-03-16 | 2021-12-22 | 藤森工業株式会社 | Laminated film and packaging bag |
| US10899521B2 (en) * | 2018-05-23 | 2021-01-26 | Johnson & Johnson Vision Care, Inc. | Package for an ophthalmic device having a multilayer lidstock containing a cyclic olefin seal layer |
| JP7107028B2 (en) * | 2018-06-29 | 2022-07-27 | 凸版印刷株式会社 | Laminates, packages and packaged articles |
| CN109628012B (en) * | 2018-12-19 | 2021-11-09 | 广东莱尔新材料科技股份有限公司 | Moisture-proof, high-temperature-resistant and low-dielectric-constant hot-melt adhesive film and preparation method thereof |
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| US5494969A (en) * | 1993-01-29 | 1996-02-27 | Mitsui Petrochemical Industries, Ltd. | Cycloolefin polymer composition |
| US6255396B1 (en) * | 1999-09-09 | 2001-07-03 | Baxter International Inc. | Cycloolefin blends and method for solvent bonding polyolefins |
| JP2003019773A (en) * | 2001-07-09 | 2003-01-21 | Fujimori Kogyo Co Ltd | Packaging film |
| DE10236502B4 (en) * | 2002-08-09 | 2004-10-14 | Nordenia Deutschland Gronau Gmbh | Sealable film for tear-open packaging |
| DE10238516A1 (en) * | 2002-08-21 | 2004-03-04 | Ticona Gmbh | Polyolefin multilayer film, process for its production and its use |
| JP4987298B2 (en) * | 2003-03-12 | 2012-07-25 | 藤森工業株式会社 | Multi-chamber container |
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| KR20090009107A (en) * | 2007-07-19 | 2009-01-22 | 도레이 카부시키가이샤 | White polyester film |
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| US20100012708A1 (en) * | 2008-07-16 | 2010-01-21 | Schlumberger Technology Corporation | Oilfield tools comprising modified-soldered electronic components and methods of manufacturing same |
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| JP5411008B2 (en) * | 2010-01-22 | 2014-02-12 | シーアイ化成株式会社 | Laminated film and packaging container produced using the laminated film |
| JP5982401B2 (en) * | 2011-12-22 | 2016-08-31 | 藤森工業株式会社 | Resin composition for sealant, laminated film and packaging bag |
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| CA2857460C (en) | 2019-08-20 |
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| KR20140121813A (en) | 2014-10-16 |
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